Simultaneous introduction of quaternary ammonium salt residues and sulfone residues into fibrous cellulose

ABSTRACT

THIS INVENTION RELATES TO A PROCESS FOR THE INTRODUCTION OF QUATERNARY AMMONIUM SALT RESIDUES AND SULFONE RESIDUES INTO FIBROUS CELLULOSE. MORE PARTICULARLY, THIS INVENTION RELATES TO A PROCESS FOR THE SIMULTANEOUS INTRODUCTION OF QUATERNARY AMMONIUM SALT RESIDUES AND SULFONE RESIDUES INTO FIBROUS CELLULOSE.

United States Patent O M US. Cl. 8188 10 ABSTRACT OF THE DISCLOSURE A non-exclusive, irrevocable, royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.

An object of this invention is to provide a simple and practical process for the preparation of cotton fabrics containing substituents bearing. quaternary ammonium salt groups and crosslinks derived from divinyl sulfone and precursors of divinyl sulfone. A further object of this invention is to prepare a cotton fabric which fabric has built-in catalysts for the thermal reversibility of crosslinkages derived from divinyl sulfone and precursors of divinyl sulfone.

It has been found that quaternary ammonium groups attached via different substituent linkages to cotton cellulose act as internal catalysts for the thermal reversibility of crosslinkages derived from divinyl sulfone. For effective introduction and removal of creases, the quaternary ammonium group is converted to the acetate salt form, and as such it provides catalysis at normal ironing temperatures without causing instability at conventional usage temperatures of conventional laundering and drying conditions. Details are described in the publication Introduction and Removal of Durable Creases from 'Wrinkle-Resistant Cotton Fabrics [Text. Res. J. 40, 607

The cotton fabrics which contain quaternary ammonium groups and sulfone residues and which are the basis 0 for the study referred to in the above manuscript were prepared as follows:

COMPOSITION, TYPE 1 (a) (CH NCH CHO'HCH substituents were intro- 5 cotton fabric.

(b) Thetertiary-amino groups were qnarternized by reaction of the DEAE-cotton with methyl iodide.

(c) The quaternary ammonium cotton (Quat 1) was converted to the base form by treatment with dilute NaOH, followed by extensive rinsing.

(d) The base form of Quat 1 was contacted with a solution of divinyl sulfone and allowed to react for 60 minutes at room temperature, or it was given a back-cure for 10 minutes at 140 C. p

Patented July 31, 1973 Details are described in the publication A Delayed Curing Cotton Fabric Based on an Internally Catalyzed Cotton Cellulose and Divinyl Sulfone [Text Res. J. 39', 173

COMPOSITION, TYPE 2 (a) (CH NCH CHOHCH -substituents were introduced into cotton fabric.

(b) The substituted cotton from (a) just above with the quaternary groups in the base form was reacted with divinyl sulfone in the same manner as described for the preceding composition.

This is described in detail in the publication Variations in a Delayed-Curing Cotton Fabric Based on Internal Catalysis and Divinyl Sulfone [Text Res. 1. 40, 101 (1970 It has now been found that the quaternary; ammonium substituent groups and\the divinyl sulfone residues can be introduced into cotton simultaneously in a single operation. The compositions which result are essentially the same as those described above iinder the heading, Composition, type 2. The compositions of type 2 as prepared by the method described above (which is that of application Ser. No. 765,613 filed Oct. 7, 1968, now US. Pat. No. 3,574,522.) could not be prepared from the more common precursors for divinyl sulfone since these require two moles of base to generate the divinyl sulfone, in addition to catalytic amounts of base for catalysis. The current invention is applicable to all of these divinyl sulfone generators which were not appropriate for the preceding case: e.g., bis(2-chloroethyl) sulfone (and corresponding bromoand iodo compounds), bis(pyridiniumethyl) sulfone dichloride, disodium bis(2-sulfatoethyl) sulfone, and disodium bis(2-thiosulfatoethyl) sulfone.

The following examples illustrate but do not limit the scope of this invention.

Example 1 A solution was prepared from 11.8 g. of divinyl sulfone, 18.8 g. of 3-chloro-Z-hydroxypropyltrimethylammonium chloride, and 13.8 g. of potassium carbonate in 55.4 g. of water. Cotton fabric x 80 printcloth, desized, scoured, bleached) was padded through this solution. The wet pickup was about The wet fabric was cured in a forced draft oven for 11 minutes at C. The fabric was rinsed thoroughly in warm running tap water, in dilute acetic acid, and finally in distilled water. After drying at room temperature, the fabric showed a 4% increase in weight over that of the initial weight. The nitrogen content was 0.32% and the sulfur content was 0.89%. This corresponds to a ratio of gram atoms of sulfurmitrogen of 1.22. The ratio may be varied over a wide range by altering the initial weight ratio of the reagents in the pad bath.

Example 2 The process described above was conducted with 11.8 g. of bis(2-hydroxyethyl) sulfone in place of the divinyl sulfone. The major difference in the product from that above was a sulfur content of 0.25% and a ratio of gram atoms of sulfurznitrogen of 0.34.

Example 3 CH OCH CH SO CH CH OCH was employed in place of divinyl sulfone in Example 1, with the addition of 10 g. of dimethyl sulfoxide to the solution. The product contained 0.3% nitrogen and 0.3% sulfur. Higher levels of nitrogen and sulfur were incorporated by conducting the cure at 180 C. for 3 minutes.

Example 4 The process of Example 1 was carried out with 15 g. of HOCH OCH CH SO CH=CH (the product from reaction of one mole of formaldehyde with one mole of divinyl sulfone; refer to US. Pat. 3,202,474) in place of thedivinyl sulfone. The nitrogen content of the fabric was 0.3% and the sulfur content was 0.65%.

Example 5 Reactions conducted as those described in Examples 1, 2, 3, and 4 but by replacing (wt. for wt.) the 3-chloro-2- hydroxypropyltrimethylammonium chloride with glycidyltrimethylammonium chloride and by using potassium carbonate, sodium carbonate, or mixtures of sodium carbonate and sodium bicarbonate for catalysis yielded generally similar results; in most cases, however, the nitrogen introduced into the fabric was approximately 25% or more higher than the values described above.

Example 6 To 11.8 g. of divinyl sulfone in 69.4 g. of water was added 18.8 g. of 3-chloro-2-hydroxypropyltrimethylammonium chloride. A sample of cotton printcloth was padded thoroughly in this solution and then it was immersed in a 6% solution of NaOH for 2% hours at room temperature. Following rinsing and drying as described for Example 1, there was observed a 9% increase in weight of the fabric. The nitrogen content was 0.17% and the sulfur content was 2.07%. The ratio of gram atoms of sulfurznitrogen Was 3.15. Potassium hydroxide is essentially equivalent to sodium hydroxide in this reaction.

Example 7 The procedure of Example 6 was conducted with 15 g. of glycidyltrimethylammoniurn chloride in place of the 3-chloro 2 hydroxypropyltrimethylammonium chloride and with 23% sodium hydroxide solution in place of the 6% solution. The cotton fabric which resulted from this reaction contained 0.43% nitrogen and 2.0% sulfur. The cellulose was converted to lattice II structure (as evidenced from X-ray diifractograms) in this case. All preceding products showed lattice I structure.

Example 8 In the manner of Example 7, separate reactions were carried out by replacing the divinyl sulfone with 15 g. of bis(2-pyridylethyl) sulfone dichloride, disodium bis(2- sulfatoethyl) sulfone, or disodium bis(2-thiosulfatoethyl) sulfone. The resulting chemically modified cotton fabrics contained about 0.25% nitrogen and the sulfur contents ranged between 2 and 3%.

Example 9 7 Cotton fabric was padded into 15.0 g. of bis(2-chloroethyl) sulfone and 15.0 g. of glycidyltrimethylamrnonium chloride in 69.4 g. of dioxane-water and the wet fabric was padded through a 12% solution of NaOH. The fabric was stored wet for 2 hours and then rinsed thoroughly in water, dilute acetic acid, and finally, water. The product fabric contained 0.2% nitrogen and 2.0% sulfur.

Example Cotton printcloth was padded into a solution of divinyl sulfone (10%) and glycidyltrimethylammonium chloride (10%) to a wet pickup of approximately 120%. The wet fabric was spread flat in an enamel pan and covered with a solution of NaOH which was just sufiicient to contact the entire fabric. The solution contained an amount of NaOH (about 3.2 g.) equivalent in moles to the glycidyltrimethylammonium chloride on 100 g. of the fabric. The fabric was continued in contact with the aqueous alkali for 3 hours at room temperature, after which it was rinsed and dried as previously described. The nitrogen and sulfur contents of the fabric were 0.3 and 1.5%s.

Example 11 Example 12 Cotton fabric was padded in a solution of divinyl sulfone (11.8%) and 3-chloro-2-hydroxypropyltrimethylammonium chloride (19%) to about wet pickup and then it was soaked in a solution containing NaOH (6%) and sodium sulfate (20%) for 2% hours at room temperature. The final nitrogen and sulfur contents of the fabric were 0.18% and 3.54%.

General comments.-All of the chemically modified cotton fabrics described in the foregoing examples exhibited improvements in conditioned and Wet wrinkle recovery angles over the values of the original cotton fabric (181 and 172, respectively, for the conditioned and wet values [W+F] for the unmodified printcloth). These values for the chemically modified cottons appeared to be primarily dependent upon the concentration of the alkali employed in the reaction as well as the temperature of the cure and the specific nature and add-on of the sulfone reagent. Wet wrinkle recovery angles in the range of 250300 are readily achieved under the conditions of reaction described above and in many cases conditioned wrinkle recovery angles in the same range are obtained (e.g., values of conditioned and wet wrinkle recovery angles of 252 and 277 for the product of Example 12).

These chemically modified cottons are valuable for their Wrinkle resistant characteristics and for their amenability to introduction and removal of creases by ironing operations as previously described [Text Res. J 40, 607 (1970) We claim: 1

1. A process of modifying a cellulosic fabric which comprises:

(a) padding a cellulosic fabric in an aqueous solution 7 containing a 3-halo-2-hydroxypropyltrimethylammonium halide or glycidyltrimethylammonium chloride, a compound selected from the group consisting of divinyl sulfone and divinyl sulfone generators, and an alkali metal base selected from the group consisting of sodium carbonate, sodium bicarbonate, mixtures of sodium carbonate and sodium bicarbonate, and potassium carbonate,

(b) curing the padded fabric from (a), and (c) washing the fabric from (b) free of excess re- OTHER REFERENCES McKelvey et al.: American Dyestulf Reporter, vol. 49, No. 22, pp. 19-24, Oct. 31, 1960.

Berni et al.: American Dyestulf Reporter, pp. 29-35, June 7, 1965.

(Other references on following page) OTHER REFERENCES Tesoro et al.: Textile Research Journal, 31, 283295 (1961).

Soignet et a1.: Textile Research Journal, 36, 978989 (1966).

Rowland et al.: Textile Research Journal, 40, 101108 (1970).

Soignet et al.: Journal of Applied Polymer Science, 13, 81-92 (1969).

GEORGE F. LESMES, Primary Examiner J. CANNON, Assistant Examiner US. Cl. X.R.

8120, DIG. 2; 260 231 A 

